WO2000006948A1 - Procede de valorisation d'un combustible par recours a des prereactions exothermiques sous forme de flamme froide - Google Patents

Procede de valorisation d'un combustible par recours a des prereactions exothermiques sous forme de flamme froide Download PDF

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Publication number
WO2000006948A1
WO2000006948A1 PCT/EP1999/005429 EP9905429W WO0006948A1 WO 2000006948 A1 WO2000006948 A1 WO 2000006948A1 EP 9905429 W EP9905429 W EP 9905429W WO 0006948 A1 WO0006948 A1 WO 0006948A1
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WIPO (PCT)
Prior art keywords
fuel
mixture
reaction
cold flame
oxidizer
Prior art date
Application number
PCT/EP1999/005429
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German (de)
English (en)
Inventor
Heinrich Köhne
Klaus Lucka
Ingo Rudolphi
Heinz-Peter Gitzinger
Lutz Hartmann
Original Assignee
Koehne Heinrich
Klaus Lucka
Ingo Rudolphi
Gitzinger Heinz Peter
Lutz Hartmann
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority claimed from DE19834051A external-priority patent/DE19834051A1/de
Priority claimed from DE19860308A external-priority patent/DE19860308A1/de
Application filed by Koehne Heinrich, Klaus Lucka, Ingo Rudolphi, Gitzinger Heinz Peter, Lutz Hartmann filed Critical Koehne Heinrich
Priority to AU60789/99A priority Critical patent/AU6078999A/en
Priority to DE59903045T priority patent/DE59903045D1/de
Priority to US09/744,752 priority patent/US6793693B1/en
Priority to EP99947264A priority patent/EP1102949B1/fr
Priority to AT99947264T priority patent/ATE225920T1/de
Priority to DE19981437T priority patent/DE19981437D2/de
Publication of WO2000006948A1 publication Critical patent/WO2000006948A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
    • C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
    • C01B3/32—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air
    • C01B3/34—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air by reaction of hydrocarbons with gasifying agents
    • C01B3/36—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air by reaction of hydrocarbons with gasifying agents using oxygen or mixtures containing oxygen as gasifying agents
    • C01B3/363—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air by reaction of hydrocarbons with gasifying agents using oxygen or mixtures containing oxygen as gasifying agents characterised by the burner used
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01B—BOILING; BOILING APPARATUS ; EVAPORATION; EVAPORATION APPARATUS
    • B01B1/00—Boiling; Boiling apparatus for physical or chemical purposes ; Evaporation in general
    • B01B1/005—Evaporation for physical or chemical purposes; Evaporation apparatus therefor, e.g. evaporation of liquids for gas phase reactions
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
    • C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
    • C01B3/32—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air
    • C01B3/34—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air by reaction of hydrocarbons with gasifying agents
    • C01B3/36—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air by reaction of hydrocarbons with gasifying agents using oxygen or mixtures containing oxygen as gasifying agents
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
    • C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
    • C01B3/32—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air
    • C01B3/34—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air by reaction of hydrocarbons with gasifying agents
    • C01B3/38—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air by reaction of hydrocarbons with gasifying agents using catalysts
    • C01B3/386—Catalytic partial combustion
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F23—COMBUSTION APPARATUS; COMBUSTION PROCESSES
    • F23C—METHODS OR APPARATUS FOR COMBUSTION USING FLUID FUEL OR SOLID FUEL SUSPENDED IN  A CARRIER GAS OR AIR 
    • F23C9/00—Combustion apparatus characterised by arrangements for returning combustion products or flue gases to the combustion chamber
    • F23C9/08—Combustion apparatus characterised by arrangements for returning combustion products or flue gases to the combustion chamber for reducing temperature in combustion chamber, e.g. for protecting walls of combustion chamber
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F23—COMBUSTION APPARATUS; COMBUSTION PROCESSES
    • F23C—METHODS OR APPARATUS FOR COMBUSTION USING FLUID FUEL OR SOLID FUEL SUSPENDED IN  A CARRIER GAS OR AIR 
    • F23C99/00—Subject-matter not provided for in other groups of this subclass
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F23—COMBUSTION APPARATUS; COMBUSTION PROCESSES
    • F23D—BURNERS
    • F23D11/00—Burners using a direct spraying action of liquid droplets or vaporised liquid into the combustion space
    • F23D11/36—Details, e.g. burner cooling means, noise reduction means
    • F23D11/40—Mixing tubes or chambers; Burner heads
    • F23D11/404—Flame tubes
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F23—COMBUSTION APPARATUS; COMBUSTION PROCESSES
    • F23M—CASINGS, LININGS, WALLS OR DOORS SPECIALLY ADAPTED FOR COMBUSTION CHAMBERS, e.g. FIREBRIDGES; DEVICES FOR DEFLECTING AIR, FLAMES OR COMBUSTION PRODUCTS IN COMBUSTION CHAMBERS; SAFETY ARRANGEMENTS SPECIALLY ADAPTED FOR COMBUSTION APPARATUS; DETAILS OF COMBUSTION CHAMBERS, NOT OTHERWISE PROVIDED FOR
    • F23M9/00—Baffles or deflectors for air or combustion products; Flame shields
    • F23M9/06—Baffles or deflectors for air or combustion products; Flame shields in fire-boxes
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/06—Combination of fuel cells with means for production of reactants or for treatment of residues
    • H01M8/0606—Combination of fuel cells with means for production of reactants or for treatment of residues with means for production of gaseous reactants
    • H01M8/0612—Combination of fuel cells with means for production of reactants or for treatment of residues with means for production of gaseous reactants from carbon-containing material
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/02—Processes for making hydrogen or synthesis gas
    • C01B2203/0205—Processes for making hydrogen or synthesis gas containing a reforming step
    • C01B2203/0227—Processes for making hydrogen or synthesis gas containing a reforming step containing a catalytic reforming step
    • C01B2203/0233—Processes for making hydrogen or synthesis gas containing a reforming step containing a catalytic reforming step the reforming step being a steam reforming step
    • C—CHEMISTRY; METALLURGY
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    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/02—Processes for making hydrogen or synthesis gas
    • C01B2203/025—Processes for making hydrogen or synthesis gas containing a partial oxidation step
    • C01B2203/0261—Processes for making hydrogen or synthesis gas containing a partial oxidation step containing a catalytic partial oxidation step [CPO]
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/02—Processes for making hydrogen or synthesis gas
    • C01B2203/0283—Processes for making hydrogen or synthesis gas containing a CO-shift step, i.e. a water gas shift step
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/06—Integration with other chemical processes
    • C01B2203/066—Integration with other chemical processes with fuel cells
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/08—Methods of heating or cooling
    • C01B2203/0805—Methods of heating the process for making hydrogen or synthesis gas
    • C01B2203/0838—Methods of heating the process for making hydrogen or synthesis gas by heat exchange with exothermic reactions, other than by combustion of fuel
    • C01B2203/0844—Methods of heating the process for making hydrogen or synthesis gas by heat exchange with exothermic reactions, other than by combustion of fuel the non-combustive exothermic reaction being another reforming reaction as defined in groups C01B2203/02 - C01B2203/0294
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/08—Methods of heating or cooling
    • C01B2203/0805—Methods of heating the process for making hydrogen or synthesis gas
    • C01B2203/085—Methods of heating the process for making hydrogen or synthesis gas by electric heating
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/08—Methods of heating or cooling
    • C01B2203/0872—Methods of cooling
    • C01B2203/0883—Methods of cooling by indirect heat exchange
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/12—Feeding the process for making hydrogen or synthesis gas
    • C01B2203/1205—Composition of the feed
    • C01B2203/1211—Organic compounds or organic mixtures used in the process for making hydrogen or synthesis gas
    • C01B2203/1235—Hydrocarbons
    • C01B2203/1241—Natural gas or methane
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/12—Feeding the process for making hydrogen or synthesis gas
    • C01B2203/1205—Composition of the feed
    • C01B2203/1211—Organic compounds or organic mixtures used in the process for making hydrogen or synthesis gas
    • C01B2203/1235—Hydrocarbons
    • C01B2203/1247—Higher hydrocarbons
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/12—Feeding the process for making hydrogen or synthesis gas
    • C01B2203/1276—Mixing of different feed components
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/12—Feeding the process for making hydrogen or synthesis gas
    • C01B2203/1288—Evaporation of one or more of the different feed components
    • C01B2203/1294—Evaporation by heat exchange with hot process stream
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/14—Details of the flowsheet
    • C01B2203/142—At least two reforming, decomposition or partial oxidation steps in series
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F23—COMBUSTION APPARATUS; COMBUSTION PROCESSES
    • F23C—METHODS OR APPARATUS FOR COMBUSTION USING FLUID FUEL OR SOLID FUEL SUSPENDED IN  A CARRIER GAS OR AIR 
    • F23C2900/00—Special features of, or arrangements for combustion apparatus using fluid fuels or solid fuels suspended in air; Combustion processes therefor
    • F23C2900/99001—Cold flame combustion or flameless oxidation processes
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F23—COMBUSTION APPARATUS; COMBUSTION PROCESSES
    • F23D—BURNERS
    • F23D2900/00—Special features of, or arrangements for burners using fluid fuels or solid fuels suspended in a carrier gas
    • F23D2900/00016—Preventing or reducing deposit build-up on burner parts, e.g. from carbon
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/06—Combination of fuel cells with means for production of reactants or for treatment of residues
    • H01M8/0662—Treatment of gaseous reactants or gaseous residues, e.g. cleaning
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E20/00—Combustion technologies with mitigation potential
    • Y02E20/34—Indirect CO2mitigation, i.e. by acting on non CO2directly related matters of the process, e.g. pre-heating or heat recovery
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/30—Hydrogen technology
    • Y02E60/50—Fuel cells

Definitions

  • the present invention relates to a method for recycling a fuel, a product obtainable according to the method according to the invention, use of the product and a device for producing a mixture for use in the method according to the invention.
  • the mixture formation of air and liquid fuels is more complex to implement than with gaseous fuels.
  • the systems work with one Atomization of the liquid and / or a thermal treatment that leads to partial or complete evaporation in air or exhaust gas.
  • Novel burner concepts for liquid fuels place very high demands on the mixture formation of fuel and air.
  • premixing concepts that implement quasi-homogeneous fuel-air mixture preparation.
  • the fuel is heated under pressure to 100 ° C. to 800 ° C. and injected into a mixing room. Due to the large pressure drop at the valve outlet, very small colloid-dispersed drops are generated compared to conventional pressure atomization, which have a certain stability due to the aggregation-inhibiting mechanisms.
  • the aerosol burner from Schilling (1997), an oil mist is generated in which heated air flows through an oil-sintered metal layer.
  • the liquid fuel is sprayed into the heated air stream using conventional pressure atomization injected and evaporated.
  • process parameters temperature, amount of air, amount of flue gas
  • a partial chemical conversion of the oil can be achieved.
  • the fuel can also be introduced into a preheated air flow and can be completely evaporated there if further heat is added. Theoretically, the temperatures required for this lead to self-ignition of the mixture. When gases such as methane (natural gas) are mixed, this risk is far less ( Figure 1).
  • the induction time described therefore represents an ignition delay. This depends on the temperature and the pressure of the mixture. So far, the results of the investigation have mainly been available under boundary conditions from the field of gas turbines and engine combustion, i.e. at elevated pressures and high temperatures. The determination of the ignition delay time is heavily dependent on the test conditions, especially the test equipment. The values given in the literature (Lefebvre, 1982; Pitsch, 1995; Spaadccini, 1982) differ accordingly. Lefebvre has for them Determination of the ignition delay times uses a tubular reactor in which the fuel injection takes place in a heated air stream and the ignition delay time is equal to the induction time until the start of the reaction (FIG. 2).
  • the technical problem underlying the invention is to overcome the disadvantages mentioned in the prior art.
  • This essentially means the mixture formation of liquid fuel and oxidizer.
  • Mixture formation is usually characterized by the superimposition of the effects of mixing, evaporation and high-temperature oxidation, which can only be separated in time and space by the ignition delay time.
  • the cold flame is also used specifically to positively influence material properties.
  • the technical problem is solved by a method for recycling a fuel that has an initial boiling temperature or predominantly an initial boiling temperature range at 1 bar between 231 K and 830 K, which is characterized by the following features:
  • the fuel is at a pressure p ⁇ 1 bar with at least one oxidizer preheated to 520 K to 880 K or at lower pressure with a lowering of the temperature range and a molar C / O- Ratio between 1: 0.14 to 1:25 brought into contact in a reaction space in such a way that exothermic prereactions in the form of a cold flame are initiated which, even with a homogeneous mixture of fuel and oxidizer, bring about only a partial conversion of the fuel and the oxidizer, and
  • step (b) by setting a technically relevant dwell time t v , the mixture produced in step a) into the reaction space, of t> 25 ms at p l l bar and dwell times which decrease with increasing pressure under otherwise identical conditions, and one limited heat removal from the reaction zone via an inert gas flow with a ratio of the heat capacity flow of the oxidizer M • c p to the product of the fuel mass flow M b and the heating value H u , which in the adiabatic reaction space M -c p / M b ⁇ H u > 2 x 10 '4 K '1 , and / or via the reactor wall with a heat flow density q of q ⁇ 85 kW / rn ⁇ a kinetic reaction inhibition of the further reaction of the oxidizable mixture formed during the cold flame occurs, thereby preventing the latter from auto-igniting, in particular for a predictable time .
  • the state parameters are understood in particular to mean the total pressure, the partial pressures of the starting materials, in particular of oxidizer and fuel, and the starting temperatures of the starting materials.
  • the process parameters include the geometrical data of the apparatus, the residence time, the wall heat flows coupled in or out via the apparatus, and the recirculation ratio from the recirculated product stream into the reaction zone to the feed stream used.
  • the residence time t v is preferably greater than 500 ms at p ⁇ 1 bar.
  • the dwell time describes the time that the mixture formed in the cold flame remains in the respective reaction space.
  • the residence time is determined by dividing the reactor volume V by the volume flow of the mixture V zxx t v - V / V. With the method according to the invention, the residence time of the mixture in the reaction space can be longer than the ignition delay time determined according to the Lefebvre method.
  • the method according to the invention uses the phenomenon of the cold flame. While the cold flame has been described in the prior art as a disadvantage that must be avoided, the phenomenon is now used in a targeted manner in the method according to the invention.
  • the method according to the invention With the method according to the invention, important processes that can currently only be operated on the basis of gases (especially natural gas) can be expanded to include liquid fuels.
  • the method according to the invention thus converts the liquid fuel phase into a gaseous phase, for example when using heating oil EL.
  • the use of a homogeneous fuel gas-air mixture enables, for example, the pollutant and noise emissions from combustion to be significantly reduced and more compact boiler systems to be used.
  • the cold flames are exothermic reactions of the liquid fuel in particular in the presence of an oxidizer, which lead to a spontaneous temperature increase of up to 180 K.
  • endothermic reactions also take place in addition to the exothermic reactions.
  • the gross reaction is exothermic.
  • Similar temperature increases can also be achieved by partial oxidation of the fuel by reducing the amount of air accordingly.
  • the difference to the cold flame reaction is among other things rem in that only a partial conversion of the oxidizer and fuel takes place in the cold flame.
  • the fuel supplied is only partially implemented, since only a limited amount of the oxidizer is present.
  • the oxidizer supplied is completely consumed in the reaction.
  • the cold flame forms a mixture of ketones, aldehydes and other compounds.
  • a defined temperature or range of the oxidizer is required to initiate the chemical reactions of the cold flame for the first time. This temperature is set as the initiation temperature. Setting data for the initiation temperature for heating oil EL are shown in FIG. 3. After initiating the cold flame, however, the operating temperature is defined. The operating temperature is understood to be the temperature which ensures stable operation of the cold flame. In practice, the range between the minimum and maximum temperature for operating the cold flame is larger than for initiating it.
  • the fuels used are essentially hydrocarbons, mixtures of hydrocarbons with non-hydrocarbons, in the form of emulsions and / or suspensions with liquids which are essentially insoluble in hydrocarbons, in particular water in a mixture with ammonia, hydrogen sulfide and / or alkanols, in particular C, -C 4 - Alkanols in question.
  • the oxidizer is a substance or a mixture of substances that has a higher chemical oxidation potential than the liquid fuel in particular.
  • Oxygen, ozone, air, exhaust gases from superstoichiometric combustion, an oxygen-containing compound such as peroxides are preferably used Compound, sulfur oxides, nitrogen oxides (N y O or NO x ) or mixtures thereof are used.
  • the temperature of 480 ° C appears to be a limit value for heating oil EL-air mixtures, because the further increase in air temperature before fuel atomization did not increase the mixture temperature. This temperature can therefore be regarded as the equilibrium temperature for the described oxidation reaction of the cold flames. At an air temperature above 480 ° C, the temperature rise of the mixture is only very small. Exothermic reactions in the form of the cold flames no longer seem to take place under the selected boundary conditions. If the air temperature is raised above 540 ° C, the mixture begins to auto-ignite, which is subject to ignition delay (see also Fig. 6).
  • the temperature profile of the cold flame along the flow path as a function of the starting temperature is shown in FIG. 4.
  • the end temperature of the cold flame is largely independent of the start temperature.
  • the initial drop in temperature before the start of the cold flame results from the enthalpy of vaporization of the liquid fuel.
  • the effects of evaporation and mixing with the oxidizer are superimposed.
  • both the injection of the liquid fuel into the air flow and the addition of pre-evaporated fuel have been investigated. It was found that the final temperatures of the cold flames reach similar values regardless of the type of fuel added.
  • the influence of the air ratio on the method according to the invention is of interest.
  • the increase in the air ratio hardly leads to changes in the final temperature of the mixture after the fuel supply.
  • a higher air ratio represents an increased ballast mass flow, which absorbs more heat when the temperature is increased by the method according to the invention.
  • 5 shows the phenomena which occur as a function of the starting conditions.
  • the square dots represent settings at the beginning of the fuel supply, which lead to the formation of a cold flame.
  • the final temperature is between 470 ° C and 480 ° C.
  • Ignition delay times of over one second can be expected below 550 ° C.
  • the course of the ignition delay time suggests a limit temperature in the technically interesting time range. Ignition can be reliably ruled out below this temperature. This makes it possible to generate a homogeneous mixture of fuel, oxidizer and cold flame products in a mixing chamber and to transport them safely.
  • FIGS. 3 to 7 show a device which is particularly suitable for carrying out the method according to the invention.
  • oxidator 2 generally means the substances which have a higher oxidation potential than fuel 1. In the usual applications, this is air or molecular oxygen, but also recycled gases from a stoichiometric combustion. However, other gases with a higher oxidation potential than the fuel, which should be recycled by the process according to the invention, such as sulfur oxides, should also be considered.
  • the fuel 1 is fed to the mixing device 6 via a fuel nozzle 7.
  • fuel 1 used here primarily includes all hydrocarbon-containing fuels, such as middle distillates or the like. In addition, this also includes mixtures of hydrocarbons with non-hydrocarbons. These are separated and fed to the process as an emulsion and / or suspension. On the one hand, the substances that are not labeled with hydrocarbons should contribute to process optimization; this is understood to mean in particular water. On the other hand, an admixture with non-hydrocarbons can be useful in order to use these additives, such as carbon, for example, by the process according to the invention.
  • the resulting fuel-oxidizer mixture flows axially from the mixing device 6 through the reaction tube 4.
  • a suitable choice of the state and process parameters is required to initiate the exothermic reactions of the cold flame.
  • the process for heating oil EL as fuel 1 and air as oxidizer 2 is to be carried out.
  • the reaction tube consists of an insulated thin-walled stainless steel tube with a length of 1000 mm and a diameter of 100 mm (see FIG. 8).
  • the oil is supplied via a conventional pressure atomization system 7.
  • the fuel output is 10 to 20 kW.
  • the air is fed to the mixing device 6 under atmospheric pressure conditions with a mixing pressure of 500 to 700 Pa.
  • the air flow must be heated accordingly to initiate the cold flame.
  • the air 2 supplied to the mixing device is heated to the initiation temperature by an air preheater.
  • an air preheater Inperiments with the adiabatic shown in Fig. 8 Cold flame generators, in which the wall heat losses are avoided by jacket heating (ideal insulation), result in a preferred range of the initiation temperature from 310 ° C to 450 ° C.
  • the cold flame manifests itself in the darkened room as a pale bluish glow and can be detected by measuring a limited rise in temperature to around 480 ° C.
  • the Cold Flame Product is a mixture that can be ignited by spark ignition.
  • air ratio ⁇ used here describes the ratio of the amount of oxygen supplied to the minimum amount of oxygen required for complete conversion of the fuel used.
  • the exothermic reactions of the cold flames cause a spontaneous temperature rise in the reaction zone 5, which can be attributed to a partial conversion of the fuel.
  • the partial conversion of the fuel is a characteristic feature of the cold flames and differentiates them from conventional combustion.
  • the oxygen present in a substoichiometric combustion with the same air ratio is completely used up (close to the detection limit).
  • the cold flame products 3 are therefore composed of the reaction products of the cold flame, but also of the starting materials which have only been partially converted, ie the fuel and oxidizer.
  • the fuel designated 1 is fed to the process in liquid or gaseous form.
  • the mixture preparation of liquid fuels represents an important problem in many technical applications. Poor atomization of liquid fuels leads to inhomogeneities in the mixture preparation and thus to the formation of pollutants.
  • the method according to the invention essentially contributes to improving the mixture formation.
  • the reaction mechanism of the cold flames causes a reduction in the molecular chain of the hydrocarbons, which contributes significantly to the lowering of the boiling temperature or the boiling temperature range.
  • the hydrocarbons used in liquid form can be converted into the gas phase, which significantly improves the mixture preparation.
  • the product After cooling to ambient temperature conditions, the product is in up to three states, in the gaseous, liquid and colloidally disperse phase (mist / aerosol).
  • the proportion of the colloidally disperse phase can predominate.
  • the method according to the invention contributes significantly to the evaporation of the liquid fuel due to its temperature level.
  • the released energy of the exothermic reaction of the cold flame supports the evaporation and generates a gas mixture which, depending on the process parameters, e.g. Heat dissipation via the outer wall of the reactor shows no autoignition under both stoichiometric and substoichiometric conditions.
  • the initiation and / or the operating temperature of the cold flames can be reduced by a number of measures.
  • the recirculation of reaction products into the reaction zone is known from combustion technology.
  • 9a to 9c based on the cold flame generator shown in FIG. 8, show three established methods for the recirculation of reaction products. In all processes, the cold flame products 3 are returned to the reaction zone 5.
  • 9a the recirculation takes place within the reaction tube 14.
  • the reaction products 3 in FIG. 9b and FIG. 9c are fed to the reaction zone 5 outside the reaction tube 4 (external recirculation).
  • 9b and 9c differ in the location of the coupling in of the reaction products 9.
  • the operating temperature of the cold flame can be reduced.
  • the liquid fuel in particular is subjected to a phase change in a mixture of air and products of the cold flame.
  • the inert gas flow increases as a result of recirculation of the cold flame products, which inhibits the tendency to self-ignition, especially for strongly substoichiometric operating modes.
  • FIG. 10 shows an exemplary embodiment for coupling the heat into the cold flame generator 10 shown in FIG. 8.
  • the cold flame product 3 leaving the cold flame generator 10 is fed to a subsequent process stage 11, the temperature of the mixture 12 emerging from the process stage 11 being above the oxidizer temperature.
  • the amount of heat required to initiate the cold flame is extracted from the mixture 12 by the oxidizer preheater 8 and fed into the oxidizer 2.
  • the heat required to reach the operating temperature is extracted directly from the cold flame product 3 and fed to the oxidizer 2 via the oxidizer preheater 8.
  • Another way of coupling heat is illustrated in FIG. 12.
  • the heat is coupled into the fuel-oxidizer mixture via the reaction tube 4 of the cold flame generator from FIG. 8.
  • the heat can be introduced, for example, by electrical heating or any desired heat capacity flow. Another form of heat coupling for fuel preheating is possible.
  • the cold flame product 3 obtained in the cold flame generator (FIG. 8) is present in the gaseous, liquid and / or colloidally disperse phase after cooling to ambient temperature. Due to the reduction in the molecular chain of the carbon chains, which is generally supported by the cold flame, the boiling temperature or the boiling temperature range of the cold flame product 3 is in any case below that of the fuel 1 used. Depending on requirements, the cold flame product 3 can be influenced by selecting the state and process parameters. For mixture preparation or synthesis gas extraction applications, it is necessary to convert the fuel largely into the gas phase. From our own experiments it is known that the end temperature of the cold flame is set to a constant value almost independently of the start temperature (see FIGS. 3 and 4). From an energetic point of view, at lower operating temperatures in the operating temperature range there is a correspondingly higher fuel consumption due to the higher temperature difference. Gas analyzes of the cold flame product confirm that a higher fuel conversion occurs in the gas phase at low operating temperatures.
  • the process according to the invention is advantageously used for the preparation and / or refinement of liquid hydrocarbons, in particular in refineries or in chemical process engineering, synthesis gas production, protective gas production, for the provision of gaseous fuels for mobile or stationary fuel cells, such as in motor vehicles, rail vehicles, ships , Aircraft and / or combined heat and power, for combustion in internal combustion engines and / or combustion plants, for separating material flows from accompanying substances and the like.
  • combustion techniques previously used exclusively for gaseous fuels are now also applicable to liquid energy sources.
  • liquid fuels is possible in innovative systems for the supply of heating and / or electrical energy, the combined heat and power generation by combined heat and power plants, because the full gasification can combine the advantage of gas engines with the lower fuel costs of liquid fuels.
  • the exhaust after treatment is through this application greatly simplified or can even be completely omitted.
  • Another example is the use in Stirling engines.
  • the cold flames can be integrated as a preliminary stage in the process of heat generation.
  • the method according to the invention can be used as a "gasifier".
  • the requirement for the supply with a homogeneous process gas with a high calorific value is fulfilled.
  • the process according to the invention produces a mixture with new properties.
  • the composition of the fuel changes due to the chemical reactions. Temperature measurements at ambient pressure and stoichiometric conditions show that, at operating temperatures around 300 ° C. and atmospheric pressure, almost 10% of the chemical energy bound in the fuel (HEL) is converted almost independently of the air ratio in the process according to the invention. Oxidation and decay reactions mainly react long hydrocarbon chains to short molecules.
  • the boundary conditions of the process can be set so that the resulting product has a significantly lower boiling range than the original fuel. This makes additional process steps possible for the use of this technology in new application areas. A limited recooling of the gas is conceivable, which enables safe handling of the mixture. Ignition according to the radical chain mechanism can be completely suppressed. This gives you the opportunity to safely transport and store the product gas from the processing process to the consumer. The modulation range can thus be decoupled from the power fluctuation of any consumer. It is also possible to control the process in such a way that even selective petrochemical building blocks (eg olefins or formaldehyde) are produced in high yield and it is interesting to separate these hydrocarbons from the product gas.
  • selective petrochemical building blocks eg olefins or formaldehyde
  • Synthesis gas is understood to mean both gas streams which are produced and used in a continuous process, and also those which are stored after generation and are used at a later point in time.
  • Endogas In material refinement (eg for metals) it is necessary, for example, to create a reducing atmosphere, a so-called endogas, which prevents oxidation of the material to be processed.
  • Endogas is usually produced by sub-stoichiometric combustion of natural gas with the addition of water.
  • the main gas components are CO, C0 2 , H 2 , H 2 0, and inert gas components.
  • the composition of the endogas can be influenced. If liquid fuels are used in substoichiometric combustion, undesirable soot formation occurs.
  • the method according to the invention enables the conversion of liquid fuels into the gas and vapor phase in a strongly substoichiometric atmosphere without noticeable soot deposits.
  • the method according to the invention is advantageously used to drive mobile devices of any kind, in particular vehicles.
  • the method according to the invention supplies processed fuels for gasoline / diesel engines and / or fuel cells.
  • the method according to the invention supplies processed fuels which are used for generating power, electricity and / or providing heat in immobile devices.
  • the processed fuels can be used in combined heat and power plants (CHPs), electricity generators, fuel cells and combustion plants.
  • CHPs combined heat and power plants
  • the gas components required for endogas production can be synthesized by adding water or steam.
  • stage (b) of the process according to the invention a further stream of material is fed to stage (b) which essentially corresponds to hydrocarbons, mixtures of hydrocarbons and non-hydrocarbons.
  • Non-hydrocarbons are understood to mean, in particular, water and / or steam in the synthesis gas production, which essentially contributes to process improvement by reducing the tendency towards soot formation.
  • air can be supplied as the non-hydrocarbon in order to achieve an air-graded combustion (air staging).
  • the cold flame is set at a low air ratio, for example at ⁇ ⁇ 1.
  • air or exhaust gas from an over-stoichiometric combustion is then added to the cold flame product.
  • 20 shows a further exemplary embodiment of a combustion process with a fuel step for nitrogen oxide reduction, in which a mixture of stage (b) from claim 1 is supplied with a further stream of material.
  • stage (b) from claim 1 is supplied with a further stream of material.
  • the sub-stoichiometrically generated cold flame product 3 is reacted with air 2 in the primary stage over-stoichiometrically with high NO production.
  • the proportion of the cold flame product introduced in this stage, based on the product generated in the cold flame generator 10, is approximately 70%.
  • the remaining cold flame product is mixed in, so that an overall reducing atmosphere is established, in which the NO formed in the first stage is then reduced to N 2 .
  • the injection and mixing of the liquid fuel into the second combustion stage is a major problem.
  • the oil injection into a hot gas stream often causes cracking reactions and deposits of oil components in the area of the oil-carrying parts and hot surfaces, which are overcome by the process according to the invention become.
  • the complete burnout takes place in the tertiary stage, where a total of over-stoichiometric conditions are set by adding so-called residual air.
  • fuel cells will become increasingly important in energy conversion systems. According to the current state of the art, these are preferably supplied with gaseous fuels to generate energy.
  • Molecular hydrogen is primarily understood as an energy source for fuel cells.
  • some fuel cells also allow the use of short-chain hydrocarbons and carbon monoxide.
  • technically complex implementation processes such as steam reforming, autothermal reforming or (catalytic) partial oxidation are required. Processes that are established on an industrial scale can be applied to those that are relevant for fuel cells Do not easily scale performance ranges. In principle, these processes lead to soot formation and, due to the high process temperatures, to reduced efficiency.
  • the method according to the invention enables the conversion of liquid fuels into the gas phase.
  • the oxygen-containing exhaust gas from the fuel cell reaction it makes sense to at least partially use the oxygen-containing exhaust gas from the fuel cell reaction as an oxidizer.
  • the product obtained from stage (b) of the process according to the invention is preferably converted by known process steps, preferably partial oxidation, steam reforming and / or the shift gas reaction (water gas reaction) into a fuel gas suitable for fuel cells, such as hydrogen, or a fuel gas mixture of hydrogen, carbon monoxide and / or short-chain hydrocarbons.
  • a fuel gas suitable for fuel cells such as hydrogen, or a fuel gas mixture of hydrogen, carbon monoxide and / or short-chain hydrocarbons.
  • 13 shows an exemplary embodiment for the conversion of liquid fuels into a fuel gas suitable for fuel cells.
  • the term fuel gas suitable for fuel cells denoted by 17 means those gas mixtures which can be used as fuel for fuel cells.
  • fuel 1 is preferably understood to mean middle distillates, such as heating oil EL, diesel, gasoline fuels, kerosene or the like.
  • the preheating can be done according to the methods described above.
  • the product mixture 3 leaving the cold flame generator 10 is used in a subsequent process step for H 2 production 15.
  • Technically known processes, such as (catalytic) partial oxidation or autothermal reforming can be connected downstream.
  • the synthesized gas mixture usually goes through a shift stage (water gas reaction) and possibly a subsequent carbon monoxide fine cleaning.
  • both reaction spaces must be separated by a fluidic and thermal decoupling.
  • the fluidic decoupling can be carried out, for example, by a flame arrester which prevents the flame from migrating back by locally increasing the mixture flow rate. root from high temperature oxidation prevented.
  • An embodiment of a flame flashback device 21 is shown in FIG. 18.
  • the thermal decoupling is intended to prevent the cold flame product from igniting on hot surfaces before entering the high-temperature oxidation. The hot surfaces can be caused by heat conduction from the high-temperature oxidation.
  • stage (b) of the process according to the invention a further stream of material is fed to stage (b), which essentially consists of hydrocarbons, mixtures of hydrocarbons and non-hydrocarbons.
  • the cold flame generator 10 can be provided with a two-stage fuel supply (see FIG. 14).
  • fuel 1 and oxidizer 2 are first fed to the cold flame generator 10 with a higher air ratio than that required for the process.
  • the second fuel injection regulates the air ratio required for the process.
  • the positive side effect of the subsequent injection of liquid fuels results from the fact that evaporative heat is removed from the mixture in the reactor and the mixture temperature is thus reduced. In this way, a re-initiation of the cold flame can be initiated, so that a further fuel conversion and thus the further gasification of the fuel can take place.
  • Water or steam feed 14 into the reaction zone of the cold flame is Another measure.
  • Water or steam are usually used in sub-stoichiometric reactions to prevent soot formation and are used simultaneously in the process according to the invention to improve the hydrogen yield.
  • the injection of liquid water causes an additional cooling of the cold flame product due to the enthalpy of vaporization, which can be expected to result in an increased fuel consumption in the cold flame due to the lowering of the starting temperature.
  • the mixture from stage (b) of the process according to the invention can at least partially be subjected to an increase in pressure.
  • Another embodiment of the method according to the invention with a subsequent pressure increase provides for use in heat engines.
  • the method according to the invention functions here for mixture preparation of the subsequent internal combustion engine 18.
  • the fuel 1, primarily a middle distillate, such as diesel, gasoline or the like, and the oxidizer 2, preferably air, are fed to the cold flame generator 10 with a technically sensible air ratio.
  • the resulting product gas mixture 3 is compressed in the following internal combustion engine 20 under petrol engine conditions and then burned.
  • the exhaust gas 19 leaving the internal combustion engine 18 serves to preheat the fuel-oxidizer mixture in the cold flame generator 10.
  • the internal combustion engine process in FIG. 17 is optimized with regard to an increase in efficiency.
  • the product mixture 3 leaving the cold flame generator 10 is pre-compressed, for example, in a conventional turbine exhaust gas charger 20 and cooled in the downstream oxidizer preheater 8, which acts as a charge air cooler.
  • the heat flow transmitted in this case serves to preheat the air 2 used.
  • the measures, turbine exhaust gas chargers in combination with charge air coolers essentially improve the degree of filling of the internal combustion engine 18 and thus at the same time that Efficiency.
  • degree of filling used in engine technology describes the ratio of the mixture volume introduced into the cylinder to the actual cylinder stroke volume, in each case based on atmospheric pressure conditions.
  • the method according to the invention makes it possible to use a uniform carburetor for different liquid fuels (e.g. gasoline, kerosene, diesel), as a result of which a multi-fuel engine can be implemented in a simple manner.
  • liquid fuels e.g. gasoline, kerosene, diesel
  • the method according to the invention enables the use of liquid fuels in applications which were previously limited to gaseous fuels.
  • the cold flame generator can be connected upstream of a turbine process in order to generate a homogeneous fuel / combustion air mixture.
  • the ignition delay time of the combustible mixture produced can be matched to the turbine process by the method according to the invention.
  • the mixture from stage (b) can at least partially be subjected to a separation process, preferably a thermal separation process.
  • the products can be influenced in a targeted manner by setting the condition and process parameters, such as temperature control, pressure, quantitative ratio of the starting materials and / or catalytic action.
  • 19 shows a substance management and substance separation process.
  • the cold flame generator 18 is followed by a separation apparatus 32 (for example phase separation, membrane separation, adsorption, absorption).
  • FIG. 18 shows a constructive embodiment of the method according to the invention in an oil burner for combustion plants with a thermal output preferably greater than 1 kW (sectional drawing).
  • the core component of the burner shown is the cold flame generator known from FIG. 8.
  • the reaction zone of the cold flame 5 is formed in the entire area of the reaction tube 4 and the annular gap formed by the burner tube 22 and the reaction tube 4.
  • the entire system is enclosed by the casing tube 23.
  • the product gas 3 is burned in the annular gap resulting between the casing tube 23 and the burner tube 22.
  • the heat required for introducing the cold flames is extracted in accordance with the preheating principle in FIG.
  • the flame holder shown at 21 serves as a backstop protection.

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Abstract

Procédé de valorisation d'un combustible qui présente une plage de température d'ébullition de sortie à 1 bar allant de 231 K à 830 K, caractérisé par les critères suivants: (a) le combustible est mis en contact, à une pression p≥1 bar, avec au moins un oxydant préchauffé entre 520 K et 880 K, dans un rapport molaire C/O situé entre 1/0,14 et 1/25, dans une chambre de réaction de manière telle que les préréactions exothermiques sous forme d'une flamme froide sont lancées, préréactions qui, même en cas de mélange homogène de combustible et d'oxydant, n'engendrent qu'une conversion partielle du combustible et de l'oxydant, (b) le réglage d'une durée de séjour techniquement appropriée tv du mélange obtenu à l'étape (a) dans la chambre de réaction de tv⊃25 ms pour p≤1 bar, et d'une évacuation limitée de chaleur de la zone de réaction par l'intermédiaire d'un flux de gaz inerte et/ou par l'intermédiaire de la paroi du réacteur, entraîne l'apparition d'une inhibition cinétique de la poursuite de la réaction du mélange oxydable obtenu par la flamme froide, un allumage spontané dudit mélange étant évité, en particulier pour une durée prévisible.
PCT/EP1999/005429 1998-07-29 1999-07-29 Procede de valorisation d'un combustible par recours a des prereactions exothermiques sous forme de flamme froide WO2000006948A1 (fr)

Priority Applications (6)

Application Number Priority Date Filing Date Title
AU60789/99A AU6078999A (en) 1998-07-29 1999-07-29 Method for utilizing a fuel by using exothermic pre-reactions in the form of a cold flame
DE59903045T DE59903045D1 (de) 1998-07-29 1999-07-29 Verfahren zur verwertung eines brennstoffs unter nutzung exothermer vorreaktionen in form einer kalten flamme
US09/744,752 US6793693B1 (en) 1998-07-29 1999-07-29 Method for utilizing a fuel by using exothermic pre-reactions in the form of a cold flame
EP99947264A EP1102949B1 (fr) 1998-07-29 1999-07-29 Procede de valorisation d'un combustible par recours a des prereactions exothermiques sous forme de flamme froide
AT99947264T ATE225920T1 (de) 1998-07-29 1999-07-29 Verfahren zur verwertung eines brennstoffs unter nutzung exothermer vorreaktionen in form einer kalten flamme
DE19981437T DE19981437D2 (de) 1998-07-29 1999-07-29 Verfahren zur Verwertung eines Brennstoffes unter Nutzung exothermer Vorreaktionen in Form einer kalten Flamme

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DE19834051.6 1998-07-29
DE19834051A DE19834051A1 (de) 1998-07-29 1998-07-29 Verfahren zur Verdampfung von flüssigen Brennstoffen zur räumlichen Trennung von Verdampfer- und Prozeßzone
DE19860308.8 1998-12-21
DE19860308A DE19860308A1 (de) 1998-12-21 1998-12-21 Verfahren zur Verwertung eines Brennstoffs unter Nutzung exothermer Vorreaktionen in Form einer Kalten Flamme
DE19927045.7 1999-06-14
DE19927045 1999-06-14

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EP (1) EP1102949B1 (fr)
AT (1) ATE225920T1 (fr)
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DE (2) DE19981437D2 (fr)
ES (1) ES2181475T3 (fr)
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US6793693B1 (en) 2004-09-21
ES2181475T3 (es) 2003-02-16
ATE225920T1 (de) 2002-10-15
DE19981437D2 (de) 2002-08-14
DE59903045D1 (de) 2002-11-14
EP1102949B1 (fr) 2002-10-09
EP1102949A1 (fr) 2001-05-30
AU6078999A (en) 2000-02-21

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